Note: Descriptions are shown in the official language in which they were submitted.
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1 H.30063
Q aternary Ammonium Compounds
THIS INVENTION relates to mixtures of
quaternary ammonium derivatives of long chain aliphatic
amines and to textile treating compositions based on
these derivatives.
Various proposals have been made for using
quaternary ammonium derivatives of long chain amines in
the formulation of compositions for treating textiles,
for example in fabric softening compositions. Although
such compositions have proved to be useful, it has been
difficult to formulate the compositions in an easily
handleable form and currently compositions tend to be
in the form of thick or semi-liquid pastes.
We have now found that certain quaternary
ammonium derivatives can be formulated into readily
; handleable compositions.
Accordingly, the present invention comprises
a composition comprising a mixture of quaternary
ammonium compounds having the general formula:
R
Rl ~ ~ R3 . X( ) in ~hich
R4
X represen-ts a qua-ternary anion, for example
chloride, bromide, iodide, methylsulpha-te,
Rl and R2, which may be the same or
different ~ithin a molecule, are long chain alkyl groups
containing from 13 to 19 carbon atoms in each group,
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the groups being both straight chain and branched and in
which the amount of branching is in the range between 30%
and 70%. Preferably the degree of branching is about 50%.
R3 and R4, which may be the same or different
within a molecule, are short chain alkyl groups
containing one to four carbon atoms in each group,
preferably methyl.
Preferably, in Rl and R2 the branching is
predominantly of 2-methyl groups.
In preferred embodiments of this invention, the
substituents R1 and R2, which may be the same or
different within a molecule, are long chain alkyl groups
containing 1~ or 15 carbon atoms in each group, the groups
being both straight chain and branched and in which the
amount of branching is in the range between 30 and 70%.
More preferably the substituents Rl and R2 are long chain
alkyl groups containing 13 or 15 carbon atoms comprising
approximately 65 to 75% C13 groups with approximately 35
to 25% C15 groups (these percentages being calculated on
the total of long chain alkyl groups) with approximately
40 to 55 wt % straight chain and 60 to 45 wt /0 2-alkyl
branched chain where the 2-alkyl group is predominantly
methyl.
Compositions according to this invention may be
prepared by the reaction of a suitable quaternising agent
R4X with either a secondary amine RlR2NH or a tertiary
amine, RlR2R3N, where Rl, R2, R3, R4 and X have the same
meaning as hereinbefore described. The secondary amine
RlR2NH may be prepared in one of a number of ways, for
~0 example (a) by heating the corresponding primary amine with
a suitable catalyst to eliminate ammonia, (b) by
alkylating a primary amine with an equimolar arnount of an
alcohol or an aldehyde, or (c) by alkylating ammonia with
two mol.e equivalents of an alcohol or an aldehyde. The
tertiary amine RlR2R3N may be prepared by, for example
(a) alkylating a secondary amine with methanol or
formaldehyde, or (b) alkylating a short chain primary amine,
for example monoe-thylamine with an alkylating agent, for
,
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example an alcohol, aldehyde, alcohol sulphate or
alkylhalide,
A particularly suitable source of primary amine
for use in the preparation of the secondary amine is a
mixture of amines, RlNH2 and R2NH2 in which Rl and R2 have
the same meaning as hereinbefore defined, and which
comprises approximately 65 to 75% C13 and approximately
35 to 25% C15 amines (these percentages being calculated
on the total of long chain alkyl groups) with approximately
~3 to 55 wt % straight chain and ~0 to 45 w-t % 2-alkyl
branched chain where the 2-alkyl group is predominantly
methyl. Such a mixture of amines which is particularly
suitable is that known as Synprolam 35 (Registered Trade
Mark).
The qua-ternised products of this invention are
highly effective fabric softeners. ~hey can be obtained
as free flowing liquids when dissolved in suitable
alcoholic solvents. The preferred solvents are lower
alcohols, for example methanol, ethanol, propanols and
butanols, the ~ore preferred solvent being isopropanol.
The preferred concentrations of the quaternised products
of this invention depend to some extent on the solubility
in the particular solvent and on -the viscosity of the
product obtained but in general it is clearly
advantageous economically to prepare a fabric softener with
as high a concentration of quaternary compound as possible.
Solutions containing less than 50% qua-ternary product are
unlikely to be attractive therefore. Compositions
containing of the order of 70 to 75 wt % of quaternary
compound in isopropanol are easily prepared and it is
believed that, if desired, compositions can be prepared
containing up to 80 to 85% of quaternary compound. The
products of the invention are also readily dispersible in
cold water to give stable dispersions which may contain,
for example 1 to 20%, and rnore preferably 4 to 10%, of
quaternary arnmonium sal-t and which may be formulated by
the addition of one or more suitable additives commonly
used in this art, for example dye, perfume, optical
.
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4 H.30063
.
brightener, and non-ionic surfactant. When so formulated,
the products OL this lnvention are particularly tJaluable
as fabric softeners and impart a softness to i`abric which
is at least as good as that imparted by prior art
formulations. Moreover, the rewettability properties of
fabrics treated with formulations incorporating the
products of this invention are superior -to those of fabrics
treated with the prior art formulations.
The products of this invention also impart
anti-static properties to synthetic fabrics, for example
*
"Nylon" and "Terylene t! .
EXAMPLE_
Secondary amine was prepared by heating a
mixture of amines, Synprolam 35 (Registered Trade Mark),
with a 50 to 55% (by weight) nickel on kieselguhr catalyst
(Girdler G493). The Synprolam 35 amine mixture had the
composition (% wt/wt~:-
n-tridecylamine 36%
2-methyldodecylamine30%
other C13 amines 3%
n-pentadecylamine 11%
2-methyltetradecylamine 16
other C15 amines 4%
~2g. of the secondary amine product was reacted
with 22g. of methyl chloride, 9g. isopropanol and 16.8g.
sodium bicarbonate a-t 123C and a pressure within the
range 260 to 300 psig for 5 hours. After filtration and
cooling, the product was a dark straw-coloured mobile
liquid containing 6.8% amine, 0.3 hydrochloride and 72.0%
quaternary ammonium compound.
EXAMPLF, 2
Secondary amine ~ras prepared by alkylating a
mixture of amines, Synprolam 35 (Registered Trade Mark),
with a C13 to C15 aldehyde having -the composition
(% wt/~,t) _
n-tridecanal 35
2-methyldodecanal 30%
other C13 aldehydes4%
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H.30063
n-pentadecanal 14,~
2-methyltetradecanal 14,6
other C15 aldehydes 4% ''
(T'nis analysis shows the composition of the
active components in the mixture relative to each other.
Small quantities of other compounds, for example
hydrocarbons, C13 to C15 alcohol may also be present).
51.6g. of the product was reacted with 43g.
methyl chloride, 135g. isopropanol and 25.5g. sodium
bicarbonate at 124C and a pressure within the range of
380 to 460 psig for 5 hours. After cooling and
filtration, the product was a straw coloured mobile liquid
containing 1.3% amine, 2.4% amine hydrochloride and 74.0~0
quaternary ammonium compound.
EXAMPLE 3
Quaternary ammonium salt prepared as in Example
1 (8g. of 72~ solution in isopropanol) was stirred cold
with a mixture of 0.0003g. dye tLissamine Blue 2BR) 0.2g.
nonionic surfactant (Synperonic*A2), O.lg. optical
brightener (Calcofluor RWP ex American Cyanamind Co),
0,15g. perfume (Lavender Floral*GC 123 ex Proprietary
Perfumes Ltd) and 91.5g, water. The product was a stable
dispersion.
Two similar formulations were prepared in which
the quaternary a~monium salt was replaced by identical
amounts of (1) dihydrogenated tallow dimethyl ar~monium
; chloride (Arquad 2THT ex Akzo-Chemie, UK Armour Hess Div)
and (2) l-tallowalkyl amidoethyl 2-tallowalkyl-3-methyl
imidazolinium methcsulphate (Varisoft 475 ex Ashland
Oil Co).
' It was necessary to heat the formulation
containing Arquad 2HT at abou-t 60C in order to obtain a
stable dispersion.
Testin,~ o~ t'ne formul~tions
(a) Treatment Sam~les of terry towellin,; were was~ed in
a conventional,detergent ~ormulation ("Tide ),
thoroughly rinsed ~,rith ~rater, and t~en imm-rsed in water
containing the particular formulat~on under tes-t at a
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. .
,
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6 H.300~3
level of 0.2 wt % of active qua-ternary ammoniurn compound
ingredient based on the weight of fabric. This procedure
was repeated until six treatments had been applied in
each case.
(b) Evaluation of Softn_ss
l~hen asked to choose the softest OI pairs of
treated fabric a panel of 14 people (as part of balanced
incomplete paired comparison tests involving other
experimental fabric softeners) gave the following choices:
_ . _
Times chosen as being
Fabric Softener Used softer than the other
sample under compari-
son
.. ~
None 3 2
Arquad 2HT 20
Varisoft 475 52
Quaternary Ammonium
compound of Ex. l 19
. _ _ _ _
(~ indicates that the judge could not
distinguish between samples).
(c) Rewettability Test
Samples of the -treated terry towelling measuring
about 25 cm x 4 cm were suspended vertically so that the
bottom 3 cm were immersed in a 0.18% w/v aqueous solution
of Lissamine Red 2G dye. The distance travelled by the dye
front up the towelling in 30 minutes was measured. The
results are as follows:
. _ __
Fabric Softener Used Distance (cm) travelled
_ . _ . . _ .
Mone 18
Arquad 2HT 17
Varisoft 475 15
Qua-ternary Arnmonium
compound of ~x. l 18
From these tests i-t is clear that compounds
according to the present invention can be formulated into
fabric softeners having excellent softening and
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rewettability properties. Moreover con-trary to some
preferences e~pressed in this art that the better fabric
softeners are those containing compounds with long chain
alkyl groups of at least 16, say 16 to 18, carbon atoms
(and preferably straight chain rather than branch chain),
-these tests show that very effective fabric softeners
can be formulated from compounds with C13 to C15 long
chain alkyl groups which have a considerable amount of
branching in them.